Alkenyloxy diarylamines



Patented' .Apr. 7; 1942 UNITED STAT- s PATENT OFFICE y g 2,273,559 I ALKENYLOXY'DIARYLAMINES Philip '1; Paul, Naugatuck, Conn., assignor to United States Rubber Company,-New York,

N. Y., a corporation of New Jersey No Drawing. Application March 16, 1939, Serial 2 Claims. (Cl. 260-571) The present invention relates to new chemicals and more especially to alkenyloxy diarylamines.

This application is a continuation-in-part of my copending application Serial No. 164,527, filed September 18, 1937.

In general, alkenyloxy diarylamines may be Y present invention are:

prepared by treating'an aromatic hydroxy material in an alcoholic sodium hydroxide solution with an alkenyl halide.

The substituted diarylamines for the purposes of the present invention, subscribe to the general formula: 4, I

where R and R. bonded to O and N, and N and X, respectively. They are preferably further unsubstituted, but may contain as further substituents in the aryl nucleus such as the following groups: amino, halogen, secondary or tertiary alkyl amino, secondary or tertiary ar'ylamino, mercapto, alkyl mercapto, etc. Y is hydrogen; is oxygen; N is nitrogen; A is an alkenyl group; X is hydrogen or an alkenyloxy group. In either or both A and X the alkenyl group may be further substituted'with maintenance of the unsaturated bond as by any 01 the following groups: halogen, amino, hydroxyl, secondary or tertiary alkyl amino, secondary or tertiary aryl amino, mercapto, alkyl mercapto, alkoxy, aryloxy.

The preferred substituted diarylamines for the purpose oi. the present invention, subscribe to the general formula:

where N is nitrogen; H is hydrogen; 0 is oxygen; R is an aromatic radical of the benzene, naphthalene or diphenyl series; R is an arylene radical singly bonded to nitrogen and oxygen respectively; and A is an alkenyl group singly bonded to the oxygen, having the general formula or in the case of an alkenyl group bearing a substituent represented by the formula:

where X may represent halogen, anilino. amino, mercapto, alkyl mercapto, etc. The aryl nuclei, R and R, may also contain substituents such as halogen, hydroxy, alkyl, aryl, amino, secondary alkyl, amino, tertiary alkyl amino. alkenyloxy', anilino, mercapto, alkyl mercapto, tertiary aryl amino, etc.

are each an aryl radical singly Examples of the chemicals included in the 2-allyloxy diphenylamine 3-allyloxy diphenylamine 4-ethyl 4'-ally1oxy diphenylamine 4-nitro 4'-a1lyloxy diphenylamine 4-ch1or 4'-allyloxy diphenylamine 2,4-diamino 4'-allyloxy diphenylamine 4-phenylamino 4'-allyloxy diphenylamine 4-isopropenyl 4-allyloxy diphenylamine Diallyloxy dinaphthylamine 3-allyloxy 5,5-dimethyl acridan 4-mercapto 4'-allyloxy diphenylamine 4-(methyl mercapto) -4-allyloxy diphenylamine 4,4'-diallyloxy diphenylamine 2,4-dimethyl '4-a.llyloxy diphenylamine 4-vinyloxy diphenylamine hydroxy, alkoxy,

i-allyloxy thio diphenylamine 4-dimethylamino 4-cinnamyloxy diphenylamine (cis and trans) 4-diphenylamino 4'-allyloxydiphenylamine 4-(4-allyloxy anilino) 4--allyloxy diphenylamine 4-methyl phenyl amino 2-allyloxy diphenylamine 2-(allyloxy'phenyl amino) naphthalene l-(cinnamyloxy phenyl amino) naphthalene 4-allyloxy diphenylamine" 2-methallylox'y diphenylamine 3-methallyloxy diphenylamine 4-methallyloxy diphenylamine 4,4'-dimethallyloxy-diphenylamine 4-crotyloxy diphenylamine 4-i'socrotyloxy diphenylamine 4-methyl vinyl carbinyloxy diphenylamine 4-(b-ethoxy) vinyloxy diphenylamine 4-allyloxy phenyl beta naphthylamine 2-al1yloxy phenyl beta naphthylamine 4-methallyloxy phenyl alpha naphthylamine 4-methy1 4'-al1yloxy diphenylamine 4-methyl 4-methal1y1oxy diphenylamine 4-dimethylamino 4-allyloxy diphenylamine 4-methyl phenylamino 4-methallyloxy diphenylamine 4-allyloxy 4'-(methyl phenyl amino) diphenylamine 4-gamma chloroallyloxy diphenylamine 4-vinyloxy-4'-phenyl diphenylamine 4-cinnamyloxy diphenylamine 4-phenoxy 4'-allyloxy diphenylamine 4-anilino-4-methallyloxy diphenylamine 4-anilino-4'-allyloxy diphenylamine 4-phenyl-4'-al1yloxy diphenylamine The following examples constitute preferred embodiments of the invention but with no inten- I of pure white crystals melting at tion to restrict the invention thereto; the parts are given by weight.

Example 1.-Preparation of 4-allyloxy diphenylamine:

i-hydroxy diphenylamine (92.5 grams) are dissolved in a mixture of 40 cc. 36% sodium hydroxide and 60 cc. alcohol and the solution heated to boiling. With stirring and heating a solution of 42 cc. allyl chloride in 40 cc. alcohol is run in over a periodof 45 minutes. Toward the end of the addition of the allyl chloride, the color lightens It is purified by recrystallizing from ligroin or alcohol.

H Analysis 7 I Melting point ..c 46-47.

Nitrogen: l i I v Theory per cent 6.23 Found do 6.12

Example 21Preparation of -methallyloxy diphenylamine: l

Y 1 i N 7 Harm...)

.4-hydroxy diphenylarnine (92.5. grams) are dissolved in a nurture of 40 cc. of 36% sodium hydroxide and 5000. alcohol, and the solution heated to reflux. with stirring and heating 60 cc. methallyl chloride is added in about to minutes. After the. addition of the halide has been completed refiuxing. minutes, and then the reaction mlxture is' poured into 1,000 cc. cold water; An oil separates which soon solidifies. After washingtwice with water, the crude product is purified by recrystallizing from alcohol, from which. it separates in the form Analysis Nitrogen: 1

Theory "per cent 5.84 Found 7 do 5.72

Example 3; Preparat ion1of i-(gamma chloro allyloxy) diphenylamine (cis-trans mixture):

4-hydroxy diphenylamine (36.3 grams) arev dissolved in a mixture of 16.8 cc. sodium is continued for i5 changed propene-1ol-3 formed by the heated to reflux. A small amount of sodium hydrosulflte is added to reduce discoloration. With stirring and heating, 18.1 cc. dichloro propene is added over a period of two'hours. Refluxing is continued for four hours after all the halide has been added. The reaction mixture is then poured into ice water, extracted with ether and the ether extract washed with dilute alkali and then with water until neutral. After evaporation of the ether, the residual oil is subjected to a steam distillation to remove any un- 1,3-dichlor propane and any l-chloro hydrolysis of 1,3-

dichloro propene. The oil is separated from the ;water and dried at 110 in vacuo. It has the following chemical and physical properties.

" Analysis Nitrogen:

Theory per cent 5.40 Found do- 5.94 Chlorine:

Theory do 13.68 Found do 12.42 Specific gravity 1.21 Index refraction 1.58 to 1.60

.as described for 'chloro allyloxy diphenylamine.

Example 4.-Preparation of a mixture of 4- methyl vinyl carbinyloxy diphenylamine:

CH: and 4-crotyloxy diphenylamine (cis-trans):

The preparation of this material is carried out the preparation of gamma 4-hydroxy diphe nylamine (46 grams) is dissolved in a mixture of 22 cc. 35% sodium hydroxide and 50 cc. alcohol and treated with 22.5 grams of a mixture of methyl vinyl carbinyl chloride and crotyl chloride. The product, after treatment with steam, isdried in vacuo at C. It amounts to 26.1 grams, and has the following physical and chemical properties.

- Analysis Nitrogen:

Theory per cent 5.84 Found -do 5.92 Index of refraction 1.627 Specific gravity 1.110

These chemicals according to the present invention may be used as insecticides, as high pressure lubricant aids, and as ,f' anti-oxidants for rubber and the like.

Having thus described my invention, what I claim'and desire to protect by Letters Patent is:

1. A -methallyloxy diarylamine.

2. 4-methallyloxy diphenylamine.

PHHJIP T. PAUL. 

